KR20100115761A - Process for producing resin composition with partial-discharge resistance, resin composition with partial-discharge resistance, and insulating material with partial-discharge resistance - Google Patents

Abstract

In a simple manner, an internally discharging resin composition having excellent partial discharge resistance and small density is produced. By inserting an organic compound by ion exchange treatment between layers of the layered clay mineral, the layered clay mineral is swelled to at least one of the polar solvent and the nonpolar solvent, and the layered clay mineral to which the swelling property is imparted is a polar solvent or a nonpolar solvent. After swelling in the swelling solvent consisting of, the epoxy resin is mixed and kneaded to remove the swelling solvent from the mixture containing the obtained epoxy resin, the layered clay mineral, and the swelling solvent, and the epoxy resin and the layered clay mineral are removed. The curing agent for epoxy resin is added and mixed to the mixture containing. As the anti-discharge insulating material which consists of the hardened | cured material of the anti-discharge discharge resin composition manufactured in this way, in the molecular chain 1 of the epoxy resin which has a three-dimensional network structure, the inorganic nanoparticle 2 which consists of layered clay minerals is It is densely and uniformly dispersed.

Description

PROCESS FOR PRODUCING RESIN COMPOSITION WITH PARTIAL-DISCHARGE RESISTANCE, RESIN COMPOSITION WITH PARTIAL-DISCHARGE RESISTANCE, AND INSULATING MATERIAL WITH PARTIAL-DISCHARGE RESISTANCE

The present invention is, for example, a method for producing an internally dischargeable resin composition for use in high voltage devices such as a generator, a rotary electric machine, a power transmission device, a water distribution device, a partial discharge resistant resin composition, and The present invention relates to an antidischarge insulating material.

The insulated coil embedded in a generator, a rotary electric machine, or the like is provided with an insulating layer for intercepting conductors and electricity between the conductors and the earth. In addition, in transmission equipment, such as a sulfur hexafluoride gas insulation switchgear and a pipeline transmission apparatus, the casting member is used as an insulation member which insulates and supports a high voltage conductor in a metal container, for example. As the insulating layer or the casting member of such a high voltage device, it is common to use an insulating resin material containing epoxy resin as a base material.

The insulation layer of an insulation coil is manufactured by impregnating the mica which consists of hard annealing mica, hard plastic mica, etc. with an epoxy resin (for example, refer patent document 1), and a mica Since itself has excellent resistance to partial discharge, internally discharging resistance is expressed also in the entire insulating layer. Moreover, an insulating spacer is mentioned as one of typical mold members, Comprising: The inorganic particle of several times of epoxy resin is filled by weight, and the necessary characteristic including the internal discharge discharge property is acquired (for example, patent documents 2 and 3). Reference).

In recent years, the case of industrial low-pressure motors and the like is accompanied by the spread of the variable speed drive by the inverter, and a case in which the motor is damaged by the inverter surge is generated. As an insulating coating material of the motor winding, There is a demand for a material having high discharge resistance. On such a point, an example in which heat-resistant partial discharge resistance is provided by depositing silica particles in a polyamideimide using a sol-gel reaction has been reported (see Patent Document 4, for example).

However, in the insulation layer of the insulation coil mentioned above, since the epoxy resin itself for impregnation has low deterioration resistance to partial discharge, the epoxy resin is selectively degraded, and the degradation gradually proceeds as a whole of the insulation layer. In addition, in the insulating spacer, since the inorganic particles are filled with the epoxy resin several times, the density of the insulating material is increased, making it difficult to reduce the weight of the high voltage device. In addition, in the method of precipitating silica particles using a sol-gel reaction, it is necessary to control the sol-gel reaction to precipitate uniform particles, which makes the manufacturing process and the manufacturing apparatus complicated, resulting in high cost.

Patent Document 1: Japanese Patent No. 3167479

Patent Document 2: Japanese Patent Application Publication No. 54-44106

Patent Document 3: Japanese Patent Application Laid-Open No. 55-155512

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-22831

[Initiation of invention]

[Problem to Solve Invention]

As described above, in the insulation layer of the insulation coil incorporated in a generator, a rotary electric machine, or the like, the partial discharge deterioration resistance of the epoxy resin for impregnation itself is low, so that the entire insulation layer also gradually deteriorates. In addition, in the insulating spacer, since the inorganic particles are filled with the epoxy resin several times, the density of the insulating material is high, and it is difficult to reduce the weight of the high voltage device. In addition, in order to deposit silica particles by using a sol-gel reaction in order to impart internal discharge resistance to an insulating coating material, there is a problem that the manufacturing process and the manufacturing apparatus are complicated and the manufacturing cost is high.

SUMMARY OF THE INVENTION The present invention has been made in order to cope with such a problem, and in a simple method, a method for producing an internally dischargeable resin composition capable of producing an internally dischargeable resin composition having excellent internal discharge resistance and a small density, and internal discharge resistance. It is an object to provide a resin composition and an anti-discharge insulating material.

[Means for solving the problem]

The manufacturing method of the internal-discharge discharge resin composition of this invention contains the epoxy resin which has two or more epoxy groups per molecule (A), the hardening | curing agent for epoxy resins, and (C) layered clay mineral as essential components. A method for producing an internally dischargeable resin composition comprising the steps of: providing an swelling property to at least one of a polar solvent and a nonpolar solvent to the layered clay mineral by inserting an organic compound between the layers of the layered clay mineral by ion exchange treatment; Swelling the layered clay mineral imparted with the swelling property in the swelling solvent comprising the polar solvent or the nonpolar solvent, and mixing and kneading the epoxy resin with the swelling solvent containing the swollen layered clay mineral. The epoxy resin obtained by the step and the step of kneading, the layered clay mineral, and the swelling And a step of removing the swelling solvent from the mixture containing the solvent and mixing the curing agent for the epoxy resin with the mixture from which the swelling solvent is removed.

Moreover, the internally discharging resin composition of this invention was manufactured by the manufacturing method of the above-mentioned internally discharging resin composition of this invention, It is characterized by the above-mentioned.

Moreover, the internal-discharge discharge insulating material of this invention consists of hardened | cured material of the above-mentioned internal discharge discharge resin composition of this invention, It is characterized by the above-mentioned.

[Effects of the Invention]

According to the present invention, since inorganic nanoparticles composed of layered clay minerals can be uniformly dispersed in an epoxy resin, an excellent internal dischargeable resin composition and a low density internally dischargeable resin composition and an internally dischargeable insulating material can be obtained. . Moreover, since no complicated manufacturing process or manufacturing method is required, it becomes possible to provide reproducibly the internally discharging resin composition and the internally discharging insulating material having excellent internally discharging properties.

[Brief Description of Drawings]

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows typically the fine structure of the internally dischargeable insulating material which concerns on one Embodiment of this invention.

FIG. 2 is a schematic diagram showing a dispersion state of inorganic nanoparticles in an internally discharging insulating material of Example 1 and an insulating material of Comparative Examples 1 to 3. FIG.

3 is a schematic diagram showing an electrode configuration used for evaluation of internal discharge characteristics.

4 is a diagram showing surface roughness after partial discharge deterioration of the internally dischargeable insulating material of Example 1 and the insulating material of Comparative Examples 1 to 3. FIG.

5 is a schematic diagram showing a state of deterioration due to partial discharge in Example 1 and Comparative Example 1. FIG.

FIG. 6 is a view showing measurement results of X-ray diffraction measurement showing a state in the epoxy resin of the layered clay mineral in Example 1 and Comparative Example 3. FIG.

7 is a schematic perspective view of an antidischarge insulating structure using an antidischarge insulating material according to the present invention.

8 is an explanatory view of another internal discharge insulating structure using the internal discharge discharge insulating material according to the present invention;

9 is a cross-sectional view of another anti-discharge insulating structure using an anti-discharge insulating material according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION [

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated. The antidispersible resin composition according to one embodiment of the present invention is an inorganic nanoparticle comprising (A) an epoxy resin having two or more epoxy groups per molecule, (B) an epoxy resin curing agent, and (C) a layered clay mineral. Particles are included as essential components.

Among the essential components of the above internally dischargeable resin composition, the epoxy resin of the component (A) is composed of an epoxy compound having two or more epoxy groups per molecule. As such an epoxy compound, if it is a compound which has two or more three-membered rings which consist of two carbon atoms and one oxygen atom in 1 molecule, and can be hardened, it can be used suitably, The kind is not specifically limited.

As a specific example of the epoxy resin of (A) component, bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, hydrogenated bisphenol obtained by condensation of polyhydric phenols, such as epichlorohydrin and bisphenol, and a polyhydric alcohol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolac type epoxy resin, phenol novolac type Glycidyl ether type epoxy resins such as epoxy resins, orthocresol novolac type epoxy resins, tris (hydroxyphenyl) methane type epoxy resins, tetraphenylolethane type epoxy resins, and condensation of epichlorohydrin with carboxylic acids Glycidyl ester type epoxy resin, triglycidyl isocyanate, epichlorohydrin and hydantoin obtained by Obtained by reaction with Hi danto there may be mentioned heterocyclic epoxy resin such as an epoxy resin, such as a doll, which are used alone or a mixture of two or more.

As a hardening | curing agent for epoxy resins of (B) component, if it can chemically react with an epoxy resin and can harden an epoxy resin, it can be used suitably, The kind is not specifically limited. As such a hardening | curing agent for epoxy resins, an amine hardening | curing agent, an acid anhydride type hardening | curing agent, an imidazole series hardening | curing agent, a polymercaptan type hardening | curing agent, a phenol type hardening | curing agent, a Lewis acid type hardening | curing agent, an isocyanate type hardening | curing agent, etc. are mentioned, for example.

Specific examples of the amine curing agent described above include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, dipropylenediamine, polyetherdiamine, 2,5-dimethylhexamethylenediamine, trimethyl Hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethyl) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, tri (methylamino) hexane, dimethyl Aminopropylamine, diethylaminopropylamine, methyliminobispropylamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) Cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, m-xylenediamine, metaphenylenediamine, Diaminodiphenylmethane, diamino And the like sulfone, diamino diethyl diphenyl methane, dicyandiamide, organic acid dihydrazide.

As an example of an acid anhydride type hardening | curing agent, dodecenyl anhydride succinic acid, a poly adipic anhydride, a polyazela dianhydride, a poly sebacic anhydride, a poly (ethyl octadecane diacid) anhydride, a poly (phenylhexadecane diacid) anhydride, a methyl tetra Hydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl himic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromelli anhydride Carboxylic acid, benzophenone tetracarboxylic acid, ethylene glycol bistrimellitate, glycerol tristrimellitate, hept anhydride, tetrabromo phthalic anhydride, nadic anhydride, methylnadic acid anhydride, polyazela anhydride and the like.

As a specific example of an imidazole series hardening | curing agent, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecyl imidazole, etc. are mentioned. Moreover, polysulfide, a thioester, etc. are mentioned as a specific example of a polymercaptan type hardening | curing agent. Any of the above-mentioned curing agents can be used alone or as a mixture of two or more kinds.

Although the compounding quantity of the hardening | curing agent for epoxy resins of (B) component is set suitably within the range of an effective amount according to the kind of used hardening | curing agent, etc., Generally, it is the range of 1/2 equivalent-2 equivalent with respect to the epoxy equivalent of an epoxy resin. It is desirable to. When the compounding quantity of the hardening | curing agent of (B) component is less than 1/2 equivalent with respect to the epoxy equivalent of (A) component, there exists a possibility that hardening reaction of the epoxy resin of (A) component cannot fully be produced. On the other hand, when the compounding quantity of the hardening | curing agent of (B) component exceeds 2 equivalent with respect to the epoxy equivalent of (A) component, basic physical properties, such as heat resistance of the hardened | cured material of an internal-discharge-discharge resin composition (epoxy resin composition), fall.

Moreover, you may use together with the hardening | curing agent for epoxy resins of (B) component, and may use the hardening accelerator for epoxy resins which accelerates or controls the hardening reaction of an epoxy resin. In particular, when an acid anhydride curing agent is used, the curing reaction is slower than other curing agents such as an amine curing agent, and therefore, a curing accelerator for epoxy resins is often used. As a hardening accelerator for an acid anhydride type hardening | curing agent, it is preferable to use a tertiary amine or its salt, a quaternary ammonium compound, imidazole, an alkali metal alkoxide, etc.

It is preferable that the compounding quantity of the inorganic nanoparticle which consists of layered clay mineral of (C) component shall be 1-50 weight part with respect to 100 weight part of epoxy resins of (A) component. If the compounding quantity of the inorganic nanoparticle of (C) component is less than 1 weight part with respect to 100 weight part of (A) components, internal-discharge discharge | distribution characteristic cannot be provided to hardened | cured epoxy resin. On the other hand, when the compounding quantity of the inorganic nanoparticle of (C) component exceeds 50 weight part with respect to 100 weight part of (A) component, the viscosity of an epoxy resin will rise and it will become difficult to uniformly disperse an inorganic nanoparticle in the epoxy resin. Moreover, hardened | cured epoxy resin becomes easily brittle, and the basic characteristic as an internal discharge-dissipative insulation material falls.

It is preferable that the primary particle diameter of the inorganic nanoparticle which consists of layered clay mineral of (C) component shall be 500 nm or less. When the primary particle diameter of the inorganic nanoparticle of (C) component is larger than 500 nm, it can provide internal-discharge discharge resistance to hardened | cured epoxy resin in the range of 1-50 weight part with respect to 100 weight part of epoxy resins of (A) component. none.

As a layered clay mineral of (C) component, at least 1 sort (s) chosen from the mineral group which consists of smectite group, mica group, vermiculite group, and mica group is mentioned, for example. Examples of the layered clay minerals belonging to the smectite group include montmorillonite, hectorite, saponite, saconite, baydelite, stevensite, and nontronite. Examples of layered clay minerals belonging to the mica group include chlorite, phlogoite, repidolite, muscobite (mica), biotite, paragonite, margarite (pearl mica), taneniolite, and tetrasilly. Food mica and the like. Examples of the layered clay mineral belonging to the vermiculite group include trioctahedral vermiculite, dioctahedral vermiculite and the like. Examples of the layered clay minerals belonging to the mica group include dolomite, biotite, paragonite, levitorite, margarite (pearl mica), cleantonite, anandite and the like. Among these, it is preferable to use the layered clay mineral which belongs to a smectite group from the point of dispersibility to an epoxy resin. These layered clay minerals can be used individually or as a mixture of 2 or more types.

Layered clay minerals have a structure in which silicate layers are stacked, and various materials such as ions, molecules, and clusters can be held by ion exchange reactions (intercalation) between the layers of the silicate layers. By using this ion exchange treatment, various metal ions and organic compounds can be intercalated between the layers of the silicate layer. By using such a property, various organic compounds can be used as interlayer materials inserted and held between silicate layers of layered clay minerals, and by using these organic compounds selectively, layered layers exhibiting swelling properties for polar solvents and nonpolar solvents can be used. Clay mineral (C) can be obtained.

The organic compound to be inserted between the layers of the silicate layer of the layered clay mineral is not particularly limited as long as it exhibits swelling property with respect to the target solvent. Preference is given to using ammonium ions.

Examples of the primary to quaternary ammonium ions include tetrabutylammonium ion, tetrahexyl ammonium ion, dihexyldimethylammonium ion, dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyltrimethylammonium ion and hexadecyl Trimethylammonium ion, stearyltrimethylammonium ion, docosenyltrimethylammonium ion, cetyltrimethylammonium ion, cetyltriethylammonium ion, hexadecylammonium ion, tetradecyldimethylbenzylammonium ion, stearyldimethylbenzylammonium ion, dioleyldimethyl Ammonium ion, N-methyl diethanol lauryl ammonium ion, dipropanol monomethyl lauryl ammonium ion, dimethyl monoethanol lauryl ammonium ion, polyoxyethylene dodecyl monomethyl ammonium ion, dimethyl hexadecyl octadecyl ammonium ion, trioctyl Methylammonium ion, tetramethylammonium ion, tetrap And the like required of ammonium ion, octadecyl ammonium ion, dimethyl octadecyl ammonium ion, dimethyl dodecyl ammonium ion. These primary-quaternary ammonium ions can be used individually or as a mixture of 2 or more types.

Moreover, in addition to (A)-(C) component as an essential component mentioned above, an internal-discharge-discharge resin composition may mix | blend the hardening accelerator mentioned above and another additive as needed in the range which does not impair the effect of this invention. Other additives to be incorporated into the antidischarge resin composition include anti-sagging agents, antisettling agents, antifoaming agents, leveling agents, slipping agents, dispersing agents, substrate wetting agents and the like.

The manufacturing method of the internal-discharge discharge resin composition which concerns on above-mentioned embodiment is demonstrated.

First, the organic compound is inserted into the layered clay mineral by the ion exchange treatment between the layers of the layered clay mineral of the above-mentioned (C) component to impart swelling property to at least one of the polar solvent and the nonpolar solvent. It is preferable to use at least 1 sort (s) chosen from the primary-quaternary ammonium ion mentioned above as an organic compound inserted between layers of layered clay mineral. Moreover, it is preferable to use the layered clay mineral whose primary particle diameter is 500 nm or less for the reason mentioned above.

Subsequently, the layered clay mineral provided with swelling property is swelled by immersing and stirring in a swelling solvent composed of a polar solvent or a nonpolar solvent, and thereafter, an epoxy resin of component (A) is further blended and kneaded. Here, it is preferable to make the compounding quantity of a layered clay mineral into the range of 1-50 weight part with respect to 100 weight part of epoxy resins for the reason mentioned above.

In addition, it is preferable to perform the kneading after the addition of the epoxy resin by applying a high shear force. Among the epoxy resins, by applying a high shear force to the layered clay minerals in which the distance between layers of the silicate layer is increased by solvent swelling, it becomes possible to more uniformly disperse the inorganic nanoparticles (layered clay minerals) in the epoxy resins.

The solvent for swelling is removed by vacuum stirring, drying, etc. from the mixture containing the epoxy resin obtained, the inorganic nanoparticle which consists of layered clay minerals, and a swelling solvent. At this time, if the washing using a low boiling point solvent compatible with the used swelling solvent and not compatible with the epoxy resin is performed in advance, the amount of the solvent removed by vacuum drying can be reduced.

Next, the target internally dischargeable resin composition is obtained by adding and mixing the hardening | curing agent for epoxy resins of (B) component to the mixture containing this epoxy resin and the inorganic nanoparticle which consists of layered clay minerals.

Moreover, by said method, from the mixture containing the epoxy resin obtained by mixing and kneading the epoxy resin of (A) component to the swelling solvent containing the swelling layered clay mineral, and the swelling solvent, Although the swelling solvent was removed and the mixture containing this epoxy resin and layered clay mineral was added and mixed with the curing agent for epoxy resins of the component (B), the swelling solvent containing the swelled layered clay mineral was mixed (B). The swelling solvent is removed from the mixture containing the curing agent for epoxy resins of the component and kneaded to obtain a curing agent for epoxy resins, a layered clay mineral, and a swelling solvent, and contains the curing agent for epoxy resins and a layered clay mineral. You may make it the target internally dischargeable resin composition by adding and mixing the epoxy resin of (A) component to a mixture.

Moreover, the epoxy number of component (B) is contained in the swelling solvent containing the swelling layered clay mineral, and the swelling solvent containing the swelling layered clay mineral mixed with the 1st mixture which mixed and kneaded the epoxy resin of (A) component. By mixing the fat curing agent to form a second mixture kneaded to remove the swelling solvent from the first mixture and the second mixture, and mixing the first mixture and the second mixture from which the swelling solvent is removed, You may make it obtain a branching resin composition.

The above-mentioned internally discharging resin composition is molded into a desired shaped body by various molding processes such as, for example, impregnation, coating, casting, sheet molding, etc., depending on the use of the insulating material. By performing the curing treatment according to the type of curing agent to the molded body and curing, an internally dischargeable insulating material is obtained. Moreover, in the manufacturing process of said internally dischargeable resin composition, the above-mentioned arbitrary components are added and mixed suitably as needed.

Thus, the internal-discharge discharge insulating material obtained is an epoxy resin having a three-dimensional network structure formed by reaction of (A) epoxy resin component and (B) hardening | curing agent for epoxy resins, for example, as shown in FIG. In the molecular chain (cured product) 1, the inorganic nanoparticles 2 made of (C) layered clay minerals are densely and uniformly dispersed. Therefore, based on the inorganic nanoparticle 2, the epoxy resin hardened | cured material which improved the internal-discharge discharge property, ie, an internal-discharge discharge insulation material, can be provided.

Moreover, since no complicated manufacturing process or manufacturing method is required, it becomes possible to provide reproducibly the internally discharging resin composition and the internally discharging insulating material having excellent internally discharging properties.

In addition, in this embodiment, by using a nanometer-size inorganic nanoparticle, since the outstanding internal discharge characteristic is expressed by the filling of a few inorganic particle with respect to an epoxy resin, and the filling amount becomes minimum, an internal discharge resistant resin composition And low density of the internally dischargeable insulating material.

The anti-discharge insulating material of the present embodiment is, for example, an insulation layer of an insulation coil used for high voltage equipment such as a generator or a rotary electric machine, an insulation film of an enamel wire used for an industrial motor, a gas insulation switchgear or a power transmission device in a pipeline. It is used suitably for the insulation support member of the high voltage conductor used for power transmission equipments (high voltage equipment), etc. The insulated coil used for a generator, a rotary electric machine, etc. is provided with the coil conductor which let high voltage electric current flow, and the insulating layer which interrupts these coil conductors, and between coil conductor and earth | ground. The insulation layer of an insulation coil can be obtained by impregnating and apply | coating an insulation resin composition to mica, for example, and hardening this. Moreover, the insulation support member of the high voltage conductor used for high voltage equipment, such as a power transmission equipment, is to insulate and support a high voltage conductor in a metal container, For example, the mold insulator which casted and hardened the insulation resin composition is used. Furthermore, the enameled wire used for an industrial motor etc. is equipped with the element wire which let a high voltage electric current flow, and the insulation film which interrupts these element wire conductors, and an element wire-ground. The insulating coating of an enameled wire can be obtained by coating an internally dischargeable resin composition and hardening this.

In addition, the internal discharge insulating material is not limited to the insulating layer of the insulating coil, the insulating film of the enameled wire, the insulating support member (mold insulator) of the high voltage conductor, and the like, and the finish varnish of the turbine end portion for the generator, the insulating rod for the circuit breaker, It can use for various uses, such as an insulation paint, a molded insulation component, the impregnation resin for FRP, and a cable coating material. In some cases, the present invention can also be applied to a high thermally conductive insulating sheet for a power unit insulating sealing material, an IC substrate, an interlayer insulating film for an LSI element, a laminated substrate, a sealing material for a semiconductor, and the like.

As described above, the internally dischargeable insulating material of the present invention can be applied to various applications. In other words, in recent years, due to the miniaturization, large capacity, high frequency band, high voltage, severe use environment, etc. of industrial and heavy electric equipment and electric and electronic equipment, internal discharge and discharge characteristics in mold insulators and impregnated insulators, etc. High performance, high reliability, high quality, and quality stabilization are required, such as improvement of the properties. The anti-discharge insulating material of the present invention meets these requirements, and by selectively using the above-described constituent materials, it is possible to use various industrial / heavy power equipments and electrical appliances as epoxy mold insulators, epoxy impregnated insulators, epoxy resin insulating films, and the like. It is possible to apply to electronic equipment.

[Example]

Next, the specific Example of this invention and its evaluation result are described.

Example 1

An intercalation process was used to insert an octadecylamine (Lion-Akuzo Co., Ltd., product name: Amine 18D) between layers of a layered clay mineral (manufactured by Kunimine Kogyo Co., Ltd., trade name: Gunipia F). After adding 10 parts by weight to 50 parts by weight of dimethylacetamide and stirring and swelling, 100 parts by weight of bisphenol A epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828) was added and preliminarily stirred. Was kneaded with high shearing force. The kneaded product was washed with a large amount of distilled water to remove dimethylacetamide, and then the remaining distilled water was removed by drying under reduced pressure to obtain a kneaded product of an epoxy resin in which inorganic nanoparticles were uniformly dispersed. 86 weight part of acid anhydride type hardening | curing agents for epoxy resins (made by Shin-Nipiya Chemical Co., Ltd., brand name: Rikaside MH-700), and the hardening accelerator for acid anhydride type hardening agents (made by Nippon Yushi Co., Ltd., brand name: M2-100) 1 weight part was added and it mixed for 10 minutes at 80 degreeC, and produced the internal-discharge discharge resin composition. By pouring this insulated resin composition into the metal mold | die heated previously at 100 degreeC, and performing a hardening process on condition of 100 degreeC x 3 hours (primary hardening) +150 degreeC x 15 hours (secondary hardening) after vacuum defoaming, An internal discharge-dissipative insulating material was produced. This internally dischargeable insulating material was used for the characteristic evaluation mentioned later.

(Comparative Example 1)

To 100 parts by weight of bisphenol-A epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828), 10 parts by weight of silica particles (manufactured by Tatsumori Co., Trade Name: Crystallite A1) having a primary particle size of 12 µm were added and kneaded. 86 parts by weight of an acid anhydride curing agent for epoxy resin (manufactured by Shin-Nip Rigaku Co., Ltd., product name: Rikaside MH-700) and a curing accelerator for an acid anhydride curing agent (manufactured by Nippon Yushi Co., Ltd., product name: M2-100) 1 A weight part was added and mixing for 10 minutes was carried out at 80 degreeC, and the internal-discharge discharge resin composition was produced. Insulating material by pouring this insulating resin composition into the metal mold | die heated previously at 100 degreeC, and hardening on condition of 100 degreeC x 3 hours (primary hardening) +150 degreeC x 15 hours (secondary hardening) after vacuum defoaming. Made. This insulation material was used for the characteristic evaluation mentioned later.

(Comparative Example 2)

To 100 parts by weight of a bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828), 200 parts by weight of silica particles having a primary particle diameter of 12 µm (manufactured by Tatsumori Co., Trade Name: Crystallite A1) were added and kneaded. 86 weight part of acid anhydride type hardening | curing agents for epoxy resins (made by Shin-Nipiya Chemical Co., Ltd., brand name: Rikaside MH-700), and the hardening accelerator for acid anhydride type hardening agents (made by Nippon Yushi Co., Ltd., brand name: M2-100) 1 weight part was added and it mixed for 10 minutes at 80 degreeC, and produced the internal-discharge discharge resin composition. By pouring this internally discharging resin composition into a metal mold | die heated at 100 degreeC previously, and performing a hardening process on the conditions of 100 degreeC x 3 hours (primary hardening) +150 degreeC x 15 hours (secondary hardening) after vacuum degassing, Insulation material was produced. This insulation material was used for the characteristic evaluation mentioned later.

(Comparative Example 3)

10 weight parts of layered clay minerals (manufactured by Kunimine Kogyo Co., Ltd., product name: Gunipia F) in which 100 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., brand name: Epicoat 828) was kept sodium ions between layers. Added and kneaded. 86 weight part of acid anhydride type hardening | curing agents for epoxy resins (made by Shin-Nipiya Chemical Co., Ltd., brand name: Rikaside MH-700), and the hardening accelerator for acid anhydride type hardening agents (made by Nippon Yushi Co., Ltd., brand name: M2-100) 1 weight part was added and it mixed for 10 minutes at 80 degreeC, and produced the internal-discharge discharge resin composition. By pouring this internally discharging resin composition into a metal mold | die heated at 100 degreeC previously, and performing a hardening process on the conditions of 100 degreeC x 3 hours (primary hardening) +150 degreeC x 15 hours (secondary hardening) after vacuum degassing, Insulation material was produced. This insulation material was used for the characteristic evaluation mentioned later.

Table 1 summarizes the differences between the inorganic nanoparticles used in Example 1 and Comparative Examples 1 to 3 described above. In addition, the dispersion state of the inorganic nanoparticles in the antidischarge insulating material and the insulating material according to Example 1 and Comparative Examples 1 to 3 was observed and investigated by transmission electron microscope (TEM) or X-ray diffraction measurement (XRD). And the schematic diagram of the dispersion state is shown to FIG. 2 (a)-(d).

TABLE 1

Next, the internal discharge discharge insulating material according to Example 1 and the insulating material according to Comparative Examples 1 to 3 were evaluated for the internal discharge discharge characteristics. As shown in FIG. 3, after grind | polishing the surface of the test piece 7 of 30 mm x 30 mm x 1 mm, it mounts on the flat-plate electrode 8, and uses the rod electrode (IEC (b)) 9, and the voltage of 6 kV. Was applied to generate a partial discharge on the surface of the test piece (7). After overtime for 48 hours, the average surface roughness of the range of 1 mm x 1 mm was measured by the laser microscope (the product name: VK-8550) from the rod electrode 9 at the position of 1 mm outside. The average surface roughness is shown in FIG. 4 as a measurement result in Example 1 and Comparative Examples 1-3.

As shown in the measurement results of the surface roughness of FIG. 4, the internally discharging insulating material according to Example 1 has a smaller roughness of the surface due to discharge than the insulating material according to Comparative Examples 1 to 3, and has excellent internally discharging discharge. It can be seen that it has characteristics. Below, the specific effect | action and effect of this invention are shown by comparatively referring Example 1 and each comparative example.

First, Example 1 is compared with Comparative Example 1. As the internally discharging insulating material according to Example 1, as the inorganic nanoparticles, 10 parts by weight of a layered clay mineral having a primary particle size of 100 nm, in which octadecylamine ions were held between layers by intercalation treatment, in advance in an organic solvent. After swelling with (dimethylacetamide), it is filled with an epoxy resin, kneaded with high shear force, and then the organic solvent is removed. On the other hand, in Comparative Example 1, 10 parts by weight of silica particles having a primary particle size of 12 µm were filled in an epoxy resin.

In the measurement results of the surface roughness of FIG. 4, when the amount of the inorganic particles is the same, it can be seen that the difference in the primary particle diameter greatly affects the internal discharge characteristics. As shown in Fig. 2 (a), as the internally discharging insulating material according to Example 1, since the nanometer-sized layered clay mineral 4 is densely dispersed in the epoxy resin 3, Fig. 5 ( As shown in a), erosion by partial discharge can be blocked and suppressed. In contrast, as the insulating material according to Comparative Example 1, as shown in FIG. 2 (b), the micrometer-sized silica particles 5 are dispersed in the epoxy resin 3. As shown, the epoxy resin 3 between the silica particles 5 is eroded by partial discharge.

As described above, as the internally dischargeable insulating material according to Example 1, excellent resistance to partial discharge is given by using nanometer-sized inorganic nanoparticles.

Next, Example 1 and Comparative Example 2 are compared. In Example 1, 10 weight part of layered clay minerals whose primary particle diameters hold | maintained octadecylamine ion between layers were filled in the epoxy resin. On the other hand, in Comparative Example 2, 200 parts by weight of silica particles having a primary particle diameter of 12 µm were filled in an epoxy resin, and as shown in Fig. 2C, the silica particles 5 having a micrometer size in the epoxy resin 3 (5). ) Are closely dispersed.

As for the degree of the surface roughness after partial discharge deterioration shown in FIG. 4, it can be confirmed that there is no big difference between the internally dischargeable insulating material by Example 1, and the insulating material by Comparative Example 2. As shown in FIG. However, when the density of the internally dischargeable insulating material according to Example 1 is compared with that of the insulating material according to Comparative Example 2, the density of the internally dischargeable insulating material according to Example 1 is 1.12 (g / cm ³ ), The density of the insulating material according to Comparative Example 2 was 1.68 (g / cm ³ ), and the insulating material according to Comparative Example 2 was 1.5 times as high as the internally dischargeable insulating material according to Example 1, indicating that the density was large.

As the internally discharge-discharge insulating material according to Example 1 as described above, by using nanometer-sized inorganic nanoparticles, 200 parts by weight of inorganic particles having a micron size were filled by filling about 10 parts by weight of inorganic particles. Since the internal discharge characteristics such as the above are expressed, and the filling amount is minimized, the density of the material can be suppressed to be small, and the weight of the insulating coil, the enameled wire, and the mold insulator can be finally reduced.

Next, Example 1 and Comparative Example 3 are compared. In Example 1, 10 parts by weight of a layered clay mineral having octadecylamine ions held between layers was swollen with an organic solvent (dimethylacetamide), mixed with an epoxy resin, kneaded with high shear force, and then filled with organic solvent to be removed. In Comparative Example 3, however, 10 parts by weight of the layered clay mineral in which sodium ions are present between the layers is mixed with the epoxy resin, kneaded with high shear force and filled. This difference greatly influences the dispersion state in the epoxy resin of the layered clay mineral. In order to grasp the dispersion state of the layered clay mineral in the epoxy resin, the surface of the internally discharging insulating material according to Example 1 and the insulating material according to Comparative Example 3 were subjected to sand paper (# 240), and then to the measurement folder. The insulating material is fixed, and the result measured in the range of 2 (theta) = 0-10 degree with the X-ray-diffraction apparatus (made by Rigaku Corporation, a model: XRD-B, CuK alpha ray) is shown in FIG.

The layered clay mineral is a sheet (silicate layer) in which SiO ₄ tetrahedra and octahedrons are arranged in a two-dimensional shape, and are fine particles having a structure in which the sheets are laminated. In the X-ray diffraction measurement, the reflection peak in the range of 2θ = 2 to 20 degrees is a peak derived from diffraction occurring between the layers of the layered clay mineral, and means that the layered clay mineral is present in the resin while maintaining the layer structure. do. In addition, when a clear reflection peak does not exist in the range of 2θ = 0 to 10 degrees, the layered clay mineral is peeled off between the layers, indicating that the peeled layers are uniformly dispersed. In the XRD measurement result of Example 1, the reflection peak does not exist in the range of 2θ = 2 to 10 degrees.

That is, in the internally discharging insulating material according to the first embodiment, as shown in Fig. 2A, the layered clay mineral 4 is peeled off between the layers and uniformly dispersed. On the other hand, in the comparative example 3, the reflection peak strong in 2 (theta) = 7 degree can be confirmed. As shown in FIG.2 (d), this shows that the layered clay mineral 6 mixed in the epoxy resin 3 exists in the epoxy resin 3, maintaining the layer structure.

In the layered clay mineral in which octadecylamine ions exist between the layers, the surface energy of the silicate layer is reduced by the octadecylamine ions, and the interlayer becomes a lipophilic atmosphere, and therefore, the swelling property to organic solvents Mars gets higher. Due to the effect of such octadecylamine ions, the interlaminar distance is widened by solvent swelling in advance, and then a high shear stress is applied and mixed with the epoxy resin, whereby the layered clay mineral is separated between the layers, and each layer is uniformly dispersed in the insulating material. . On the other hand, in Comparative Example 3, since sodium ions are present between the layers of the layered clay mineral, the affinity for the epoxy resin is low. For this reason, even if high shear stress is applied and mixed, layered clay minerals cannot be uniformly dispersed in an insulating material.

As in Example 1, the layered clay mineral uniformly dispersed in the epoxy resin can impart excellent internal discharge characteristics to the epoxy resin in order to suppress degradation due to partial discharge, and thus the surface after partial discharge degradation shown in FIG. 4. The illuminance is reduced.

7 to 9 each show an example of an internal discharge insulating insulating structure using the internal discharge insulating insulating material according to the present invention.

7 is a diagram showing an insulated coil used in high voltage equipment such as a generator and a rotary electric machine. In FIG. 7, the insulating layer 12 which interrupts coil conductors 11 and coil conductors 11-earth is provided in the circumference | surroundings of the coil conductor 11 which flows a high voltage electric current. Here, the insulating layer 12 is formed by, for example, impregnating and applying the internally discharging resin composition according to the present invention to mica, and curing this.

8 is a diagram showing an insulating member used in the gas insulated switchgear. In FIG. 8, the conductor 13 which flows a high voltage electric current is insulated and supported by the insulating member 15 in the metal container 14 in which the insulating gas (sulfur hexafluoride gas) was enclosed. Here, the insulating member 15 consists of the mold insulator which casted and hardened the internal-discharge-discharge resin composition which concerns on this invention.

9 is a cross-sectional view showing an enameled wire used for an industrial motor and the like. An insulation film 17 is provided around the wire conductors 16 through which the high voltage current flows, and the wire conductors 16 and the wire conductors 16 and the earth are intercepted. The insulating protective film 18 is provided in the circumference. Here, the insulating film 17 can be obtained by coating the internally discharging resin composition according to the present invention and curing it.

According to the anti-discharge insulating structure using the anti-discharge insulating material which concerns on this invention as shown to FIGS. 7-9, the characteristic and reliability of a high voltage device can be improved.

In addition, this invention is not limited to the said embodiment as it is, In an implementation step, a component can be modified and actualized in the range which does not deviate from the summary. In addition, various inventions can be formed by appropriate combinations of a plurality of components disclosed in the above embodiments. For example, some components may be deleted from all the components shown in the embodiment. Moreover, you may combine suitably the component over other embodiment.

ADVANTAGE OF THE INVENTION According to this invention, the internal-discharge-proof resin composition and the internal-discharge-proof insulation material which have outstanding internal-discharge discharge property and a small density can be obtained, The internal-discharge-discharge insulation material of this invention is an epoxy mold insulator, an epoxy impregnated insulator, As an epoxy resin insulating film etc., it can apply to various industrial and heavy electric appliances, and an electrical and electronic equipment.

Claims (6)

(A) As a manufacturing method of the epoxy resin which has two or more epoxy groups per molecule, (B) hardening agent for epoxy resins, and (C) layered clay mineral as an essential component, ,
Providing an swelling property to at least one of a polar solvent and a nonpolar solvent to the layered clay mineral by inserting an organic compound between the layers of the layered clay mineral by ion exchange treatment;
Swelling the layered clay mineral imparted with swelling property in the swelling solvent comprising the polar solvent or the nonpolar solvent;
Mixing and kneading the epoxy resin in the swelling solvent containing the swelling layered clay mineral;
Removing the swelling solvent from the mixture containing the epoxy resin, the layered clay mineral, and the swelling solvent obtained by the kneading step;
Mixing the curing agent for the epoxy resin with the mixture from which the swelling solvent is removed
Method for producing a partial discharge resistant resin composition comprising a. The method of claim 1,
The layered clay mineral is composed of at least one selected from a mineral group consisting of smectite group, mica group, vermiculite group, and mica group. The method of claim 1,
In the step of imparting swelling property, the organic compound inserted between the layers of the layered clay mineral is at least one selected from primary to quaternary ammonium ions. The method of claim 2,
In the step of imparting swelling property, the organic compound inserted between the layers of the layered clay mineral is at least one selected from primary to quaternary ammonium ions. It is manufactured by the manufacturing method of the internal-discharge discharge resin composition of Claim 1 or 4, The internal-discharge discharge resin composition characterized by the above-mentioned. It consists of hardened | cured material of the internal-discharge discharge resin composition of Claim 5, The internal-discharge discharge insulating material characterized by the above-mentioned.

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